Rhodium-Catalyzed Pauson–Khand Reaction Using a Small-Bite-Angle P‑Stereogenic C 1‑Diphosphine Ligand

Rhodium-Catalyzed Pauson–Khand Reaction Using a Small-Bite-Angle P‑Stereogenic C 1‑Diphosphine Ligand

The asymmetric Pauson–Khand reaction catalyzed by [Rh­(COD)­(MaxPHOS)]­BF4 is described. Several 1,6-enynes have been chosen as model substrates affording moderate yields and selectivities of up to 86% ee. Besides binap-type ligands, we have demonstrated that the P-stereogenic C 1-symmetry small-bit...

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Bibliographic Details
Published in:Organometallics Vol. 34; no. 20; pp. 4989 - 4993
Main Authors: Cristóbal-Lecina, Edgar, Costantino, Andrea R, Grabulosa, Arnald, Riera, Antoni, Verdaguer, Xavier
Format: Journal Article
Language:English
Published: American Chemical Society 26-10-2015
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Summary:The asymmetric Pauson–Khand reaction catalyzed by [Rh­(COD)­(MaxPHOS)]­BF4 is described. Several 1,6-enynes have been chosen as model substrates affording moderate yields and selectivities of up to 86% ee. Besides binap-type ligands, we have demonstrated that the P-stereogenic C 1-symmetry small-bite-angle ligand MaxPHOS is a viable ligand in this process. The formation of [2+2+2] cycloaddition compounds has shown to be a competitive process. A mechanism is proposed to account for the observed results. The intermediate rhodium dicarbonyl complex 6 was synthesized, and its solid-state structure was elucidated by X-ray crystallography.
ISSN:0276-7333
1520-6041
DOI:10.1021/acs.organomet.5b00576